Halo-substituted vinyl phosphate pesticides



United States Patent 3,259,542 HALO-SUBSTITUTED VINYL PHOSPHATE PESTICIDES Everett E. Gilbert, Morris Township, Morris County, Julian A. Otto, Lake Tamarack, and John J. Donleavy, North Caldwell, N.J., assignors to Allied Chemical Corporation, a corporation of New York No Drawing. Original application Nov. 22, 1957, Ser. No. 698,046, now Patent No. 3,207,776, dated Sept. 21, 1965. Divided and this application Mar. 26, 1965, Ser.

8 Claims. (Cl. 167--22) This is a division of application Serial No. 698,046 filed November 22, 1957, now US. Patent No. 3,207,776.

This invention relates to the production of new halosubstituted vinyl phosphates useful as active insecticidal and Initicid-al toxicants.

These new halo-substituted vinyl phosphates conform to the general formula:

R! l] (Ro),P-o0

in which R is an alkyl radical, particularly an alkyl radical containing from 1 to 4 carbon atoms, R is a member of the group consisting of hydrogen, and alkyl, chloro-substituted alkyl, fluoro-substituted alkyl and chlorofiuoro-substituted alkyl radicals, particularly chloromethyl, fluorornethy-l or chloirofluoromethyl, and R" is a member of the group consisting of chloro-substituted alkylene, fluoro-substituted alkylene and chlorofluorosubstituted alkylene radicals, particularly chloromethylene, fluoromethylene or chloroflu-oromethylene, R and R" taken together containing at least one fluorine atom.

In the new compounds, .typical examples of R are CH C H and (CH CH. Typical examples of R are H, CH C01 CCl- 'F, CClF CR, and CHF Typical examples of R" are CCI CF CO1]? and CI-lF.

Halo-substituted vinyl phosphates of the general formula given above may be prepared according to certain aspects of the invention by reacting a fluoroor chlorofluoro-substituted .aldehyde or ketone with a dialkyl phosp'hite to form an intermediate phosphonic ester. When the intermediate phosphonic ester is prepared from a Cll'lOI'OflllOflTO S lIbSiiiill-lCd aldehyde or ketone, the intermediate phosphonic ester may be distilled under reduced pressure to convert the ester into the corresponding chlorofluoro-substituted vinyl phosphate. Alternatively, in place of conversion by distillation procedure, the intermediate phosphonic ester may be treated with an inorganic or organic base such as sodium hydroxide or pyridine, whereby it is converted into the desired chlorofluoro-substituted vinyl phosphate. In the case of an intermediate phosphonic ester prepared from a fluoro-substituted aldehyde or ketone containing no chloride atom, the intermediate phosphonic ester must be subjected to the treatment with a base in order to convert it into the corresponding fluoro-substituted vinyl phosphate.

The reaction between the chlorofluoroor fluoro-substituted aldehydes or ketones .and dialkyl phosphites to form the desired vinyl phosphates of the present invention may be represented by .the following equations. In the equations R, R and R" have the meanings shown above, R'" is a member of the group consisting of chloro-substituted alkyl, fiuoro-substituted alkyl and 3,259,542 Patented July 5, 1966 chlorofiuoro-substituted alkyl radicals, and R and R taken together contain at least one fluorine atom.

intermediate ph sph nic ster 0 R ll vinyl phosphate compound d stillation In this reaction, lay-product HCl is obtained from chlorofluoro-substituted aldehydes or ketones, while by-product HP is obtained from fluoro-substituted aldehydes and ketones containing no chlorine atoms.

According to other aspects of the present invention, chlorofiuoro-substituted vinyl phosphates may be prepared by reacting a chlorofluoro-substituted aldehyde or ketone with a trialkyl phosphite. In this reaction, the

intermediate phosphonic ester is transitory and breaks 1 down, Without further treatment, into the desired chlorofluoro-substituted vinyl phosphate. These reactions may be represented by the following equations. In the equations R, R and R have the meanings shown above, R'" is a member of the group consisting of chloro-substituted alkyl, fluoro-substituted alkyl and chlorofluorosubstituted alkyl radicals, and R and R taken together contain at least one chlorine atom and at least one fluorine atom.

Although the substituted aldehydes or ketones and alkyl phosphites may be charged in molar proportions of one mol of substituted aldehyde or ketone to about 0.5 to 1.5 mols of dialkyl or trialkyl phosphite, approximately equimolar proportions of the reactants are preferred.

If desired, the present reactions may be carried out in the presence of an inert organic solvent, preferably one lower boiling than the vinyl phosphate produced. Suitable inert organic solven-ts'include methylene chloride, ethyl ether, acetone and benzene. When the reactions are completed, lower boiling solvent so used may be recovered for reuse by simple distillation at atmospheric or lower pressure.

The reactions may be carried out at any temperature up to the decomposition point of the reactants, and are preferably carried out at about 10 to C. Generally, the reaction is quite vigorous during the addition of the reactants, and cooling is desirable to retard the reaction. As is apparent from the above equations illustrating the reaction of the substituted aldehydes or ketones with .alkyl phosphites, hydrogen chloride or fluoride (in the case of the dialkyl phosphite reactants) or alkyl chloride (in the case of the trialkyl phosphite reactants) are formed. These by-products may be readily removed from the reaction mixtures by simple distillation procedures. The hydrogen chloride of fluoride may be conveniently collected in a water trap connected to the vessel in which reaction takes place.

The following examples are given for the purpose of illustrating the present invention but are not intended to be limiting on the scope thereof. Parts are by weight.

Example 1.108 parts of trichlorotrifiuoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 69 parts of diethyl phosphite were added dropwise over a 20-minute period with stirring and cooling to maintain the temperature of the reaction mixture at 20 C.- (i C.). Stirring of the reaction mixture was continued for 2 hours at room temperature, and it was allowed to stand overnight. The reaction mixture was then vacuum distilled. A liquid comprising the chlorofiuoro-substituted vinyl phosphate, having the following formula, distilled over at 84 to 86 C. (1.5 mm. mercury pressure):

H /C C11: (CzHsO)2P-OC CClF The vinyl phosphate product constituted 102 parts (64% of theory).

Example 2.116 parts of tetrachlorodifiuoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 83 parts of triethyl phosphite were added dropwise over a 40-minute period with stirring and cooling to maintain the reaction mixture at a temperature of 20 C. (:5" C.). The reaction mixture was stirred for 2 hours at room temperature and was allowed to stand overnight. The reaction mixture was then slowly warmed under reduced pressure to remove ethyl chloride formed during the reaction. Finally, the reaction mixture was vacuum distilled. A liquid comprising the chlorofluoro-substituted vinyl phosphate having the following formula distilled over at 111 to 112 C. (2.5 mm. mercury pressure):

The vinyl phosphate product constituted 161.5 parts (97% of theory).

Example 3.124.3 parts of pentachloromonofluoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 62 parts of triethyl phosphite were added dropwise over a 35-minute period with stirring and cooling to maintain the temperature at 20 C. (15 C.). The reaction mixture was then allowed to stand at room temperature for 40 hours. Ethyl chloride formed during the reaction was stripped oif under reduced pressure. The reaction mixture was then vacuum distilled. A water-white liquid comprising the chlorofiuoro-substituted vinyl phosphate having the toll-owing formula distilled over at 128 to 130 C. (1.5 mm. mercury pressure):

fl) CClzF (CzH50)2P-O-C C012 147 parts of the vinyl phosphate product were obtained, the yield being 91.3% of theory.

Example 4.-100 parts of pentachlorornonofiuoroacetone were put in a reaction vessel provided with a stirrer and an ice bath. 50 parts of trimethyl phosphite were added dropwise over a period of 45 minutes with stirring and cooling to maintain the temperature of the reaction mixture at 20 C. (:5 C.). The reaction mixture was allowed to stand at room temperature for several days and, after stripping off byproduct methyl chloride under reduced pressure, was vacuum distilled. 1175 parts of 4 a water-white liquid comprising the chlorofluoro-substituted vinyl phosphate having the following formula distilled over at 113 to 115 C. (1.5 mm. mercury pressure):

H /CC1zF (CHrO)2P-OO CCl:

The yield of the vinyl phosphate product obtained was 91% of theory.

Example 5.139 parts of tetrachlorodifiuoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 66 parts of dimethyl phosphite were added dropwise with stirring and cooling to maintain the reaction mixture at 10 C. (12 C.). The reaction mixture was allowed to stand at room temperature for a few days. The reaction mixture was then vacuum distilled. The distillate coming over at about 97 C. (2.2 mm. mercury pressure) was a liquid comprising the chlorofiuoro-substituted vinyl phosphate having the following formula:

54 parts of the vinyl phosphate product were collected, constituting a yield of 29% of theory.

Example 6.116 parts of tetrachlorodifluoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 62 parts of trimethyl phosphite were added dropwise over a 1 hour period with stirring and cooling to maintain the temperature of the reaction mixture at 20 C. (:5 C.). The reaction mixture was allowed to stand at room temperature for several days. After stripping off byproduct methyl chloride under reduced pressure, the reaction mixture was vacuum distilled. 147 parts of a water-white liquid comprising the following chlorofluoro-substituted vinyl phosphate distilled over at 90 to 92 C. (1.5 mm. mercury pressure):

C ClF (6) The vinyl phosphate product yield constituted 96% of theory.

Example 7.129 parts of trichlorotrifiuoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 66 parts of dimethyl phosphite were added dropwise over a 20-minute period with stirring and cooling to maintain the temperature of the reaction mixture at 10 C. (12 C.) After addition of the dimethyl phosphite, stirring was continued for 35 minutes with the cooling bath removed. The mixture was allowed to stand overnight and was then vacuum distilled. 96 parts of a liquid comprising the following chlorofiuoro-substituted vinyl phosphate distilled over at 83 to C. (2.5 to 3 mm. mercury pressure):

CCIF 7) The amount of vinyl phosphate product collected represented 55% of theory.

Example 8.l08 parts of trichlorotrifiuoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 83 parts of triethyl phosphite were added dropwise over a 40-minute period with stirring and cooling to maintain the temperature of the reaction mixture at 20 C. (15 C.). The reaction mixture was stirred for 2 hours at room temperature and allowed to stand overnight. Ethyl chloride by-product was stripped off at reduced pressure, and the reaction mixture was then vacuum distilled. 94 parts of a liquid comprising the following chlorofluoro-substituted vinyl phosphate distilled over at 82 to 84 C. (1.4 mm. mercury pressure):

it (CZH O)QP-OO The amount of vinyl phosphate product collected constituted 87% of theory.

Example 9.120 parts of dichlorotetrafluoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 66 parts of dimethyl phosphite were added dropwise with stirring and cooling to maintain the temperature at 10 C. (12 C.). The reaction mixture was allowed to stand for a few days and then was vacuum distilled. 67 parts of a light yellow oil comprising the following chlorofiuoro-substituted vinyl phosphate were collected at 70 to 72 C. (4.2 mm. mercury pressure):

a) (CH3O)2POO\ CFz 9) The amount of vinyl phosphate product collected comprised 41% of theory.

Example 10.99.5 parts of dichlorotetratluoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 69 parts of diethyl phosphite were added dropwise over a 20-minute period with stirring and cooling to maintain the temperature of the reaction mixture at 20 C. (i5 C.). The reaction mixture was stirred for 2 hours at room temperature and allowed to stand overnight. The reaction mixture was then vacuum distilled. 111 parts of a liquid comprising the following chlorofluoro-substituted vinyl phosphate compound distilled over at a temperature of 80 to 81 C. (3.5 mm. mercury pressure):

The amount of vinyl phosphate product recovered represented 74% of theory.

Example 11.99.5 parts of dichlorotetrafluoroacetone were placed in a reaction vessel provided with a stirrer and an ice bath. 83 parts of triethyl phosphite were added dropwise over a 20-minute period with stirring and cooling to maintain the temperature of the reaction mixture at 20 C. (15 C.). The reaction mixture was stirred for 2 hours at room temperature and allowed to stand overnight. By-product ethyl chloride was stripped oil at reduced pressure, and the reaction mixture was then vacuum distilled. 145 parts of a liquid comprising the following chlorofluoro-substituted vinyl phosphate compound distilled over at a temperature of 75 to 76 C.

(3 mm. mercury pressure):

(H) CClFz (C2H5O)2COC CFZ 11) The amount of vinyl phosphate product recovered represented 96% of theory.

Example 12.A solution of 55 parts of dimethyl phosphite in 100 parts of methylene chloride were placed in a reaction vessel provided with a gassing tube, a stirrer and an ice bath. 91.5 parts of chloropentafiuoroacetone in nitrogen as carrier were bubbled into the solution over a 1% hour period, maintaining the temperature of the solution at about 10 C. (i5 C.). The ketone had been liquefied at Dry-Ice temperature and was allowed to boil off into a slow stream of nitrogen. The reaction mixture was stirred for 1% hours, allowing it to come to room temperature, and was then allowed to stand overnight. The methylene chloride solvent was stripped oil on a steam bath at reduced pressure, and the residue was then vacuum distilled. 80.5 parts of a liquid comprising the following fluoro-substituted vinyl phosphate compound distilled over at 41 to 45 C. (1.5 to 2.5 mm. mercury pressure):

CFz

The amount of vinyl phosphate product recovered constituted 63% of theory.

Example 13.110 parts of dimethyl phosphite in 310 parts of methylene chloride were charged into a reaction vessel 'equipped with a gassing tube, a stirrer, a reflux condenser and a drying tower at the exit of the condenser. 114.5 parts of chlorodifluoroacetaldehyde were introduced through the gassing tube mixed with nitrogen as it was generated in another reaction vessel. (The chlorodifluoroacetaldehyde was obtained by dropping chlorodifluoroacetaldehyde hydrate in concentrated sulfuric acid (96%) warmed to about 50 C., and then distilling oi the aldehyde.) During addition of the aldehyde, the reaction vessel was maintained at a temperature of 25 to 35 C. The reaction mixture was stripped free of methylene chloride at reduced pressure and was then vacuum distilled (3 mm. mercury pressure). 188 parts of residue were obtained.

94 parts of the residue were added to about 1200 parts of water with stirring. 20 parts of sodium hydroxide in about 100 parts of Water were then slowly added with continued stirring. The aqueous mixture was extracted four times with a total of about 500 parts of ether. After drying the extract over anhydrous sodium sulfate, ether Was evaporated. The residue was then subjected to vacuum distillation. A liquid comprising the fluoro-substituted vinyl phosphate'having the following formula distilled over at 58 C. (3 mm. mercury pressure):

Example 14.39 parts of tetrafluoroacetone were placed in a reaction vessel provided with a stirrer. 33 parts of dimethyl phosphite were added dropwise over a period of 10 minutes with stirring, while maintaining the temperature of the reaction mixture at 30 C. (i5 C.). The reaction was continued for about 20 minutes, holding the temperature at 40 to 45 C. The reaction mixture 7 was allowed to stand at room temperature for a few days and was then heated to C. at 2.5 mm. mercury pressure. The residue comprised 69 parts of the following intermediate phosphonic ester:

CHFz CHF Example 15.55 parts of dimethyl phosphite were charged into a reaction vessel provided with a gassing tube, a stirrer and a Dry Ice-cooled condenser. 66 parts of trifluoroacetone gas were fed into the vessel through the gassing tube. The temperature of the reaction mixture rose to 34 C. and was held relatively constant by the trifluoroacetone reflux, the rate of which increased as it (CH OhP-O-C more trifiuoroacetone was added. The reaction mixture was then heated at refiux for hours, the temperature being maintained at about 34 C. The reaction mixture was allowed to stand overnight and was then heated at re- 8 sprays or dust compositions and the amount of toxicant used may vary, a sufiicient quantity being utilized to provide the required toxicity.

When employed in the form of a powder or dust for duced pressure. First, unreacted trifiuoroacetone (36 5 killing insects and mites, the above compounds or toxiparts) was stripped off. Then, the reaction mixture was cants may be mixed with a substantial proportion of any vacuum distilled at 2.5 mm. mercury pressure. 38 parts suitable inert material or diluent, preferably in finely didistilled over at 38 to 51 C., and the residue comprised vided form, such as known grades of prepared paraciti- 32.5 parts of the following intermediate phosphonic ester: cide carrier clays, pyrophyllite, fullers earth, bentonite,

0 CH3 0 sulfur, lime, talc, whiting, diatomaceous earth, etc. Suitll I able dusts of this type usually contain not less than 0.25% (CHSOM I and preferably not less than 0.5% by weight of toxicant.

C F: Liquid insecticide or miticide sprays containing the toxi- The unreacted trifluoroacetone and the distillate from cant P the lnyentloll y f P pa y first forming a the vacuum distillation were combined, returned to the 15 Solutlon of the compound In a Sultable f Solvent, reaction vessel and again heated at reflux. Starting at 37 y mfithylatefl 11229312116965 Or y hlghly C., the temperature slowly rose after hours to 60 C., fnatlc l yp msecilclde f Preferably and after 11 hours to 75 C. The reaction mixture was mg a Small amount of Wetting emulslfylng agent then held at a temperature of 75 C. c.) for 6 y p y in the such as dlglywl oleate or hours and was distilled as above. The residue comprised P- y Pheny1 ether p ly f y y The 58 parts f th bo i t di t phosphonic ester d sulting concentrate solution is incorporated with water was bi d h i h in quantity suflicient to form an aqueous spray dispersion To 44,4 parts of the phesphonic ester w dd d b t or emulsion having the desired active ingredient concen- 200 parts of 1.0 N sodium hydroxide. The phosphonic Tratlollester slowly dissolved, and an oil gradually separated. In a P embodlmem, q f p y dlsPel'slons After one day, 15 parts of the oil had separated. This of em}11$10I1S y be formed 'y Incorporating 111 Wafer oil comprised the following fluoro-substituted vinyl phosf y mlXtufeS 0f SCI-Called Wettable P y Powders i h t mg the phosphate products of the invention. These lIllX- CH3 tures may also include inert diluents, suitable quantities I! of wetting or emulsifying agents, and if desired, secondary (CH O)1POC toxicants.

CFZ (15) The aqueous spray dispersions of the invention prefer- As indicated above, the vinyl phosphate compounds of ably should contain the active ingredient in an amount not this invention find valuable application as active insectiless than A of a pound per 100 gallons of spray, the more cidal and miticidal toxicants. These compounds are ordiusual concentrations being in the range of to A of a narily applied as toxicants for combating insect and mite pound per 100 gallons of spray. pests, in conjunction with a carrier which may be a solid, Insecticidal and miticidal properties of vinyl phosphate liquid or gaseous material. The vinyl phosphate comcompounds typical of those embraced within the scope pounds may be employed either in the form of aqueous of this invention are indicated in the following table:

Halo-Substituted Housefly Mite Kill, Vinyl Phosphate Formulation Kill Iger- Percent 2 con 1 Compound (1) 0.4% vinyl phosphate composition, 20% 100 Karo syrup (a commercial corn syrup), 79.6% water. Compound (2) 0.25% vinyl phosphate composition, 81. 5

20% Karo syrup, 79.75% water. Compound (3) 0.25% vinyl phosphate composition, 94.4

20% Karo syrup, 79.75% water. Compound (4) 0.25% vinyl phosphate composition, 100

20% Karo syrup, 79.75% water. Compound (5) 0.0125% vinyl phosphate compound, 96.1

2.5% Karo syrup, 97.48% water. Compound (5) pt. vinyl phosphate compound 4 per 97.8 (2 days).

100 gals. water. Compound (6) 0.25% vinyl phosphate composition; 100

20% Karo syrup, 79.75% water. Compound (7) 0.1% vinyl phosphate compound, 10% 100 Karo syrup, 89.9% water. Compound (7) 1 pt. vinyl phosphate composition 3 per 96.6 (3 days).

100 gals. water. Compound (8) 0.4% vinyl phosphate composition, 20% 100 Karo syrup, 79.6% water. Compound (9) 0.1% vinyl phosphate compound, 10% 100 Karo syrup, 89.9% water. Compound (10).-." 04% vinyl phosphate composition, 20% 100 Karo syrup, 79.6% water. Compound (l1) 0.4% vinyl phosphate composition, 20% 190 Karo syrup, 79.6% water. Compound (13)- 1 pt. vinyl phosphate composition 3 per 98.7 (3 days).

100 gals water. Compound (14) 1 part by volume of a solution of vinyl 98.9 (3 days).

phosphate compound in acetone 5 per 319 parts by volume of water.

I The tests on toxicity to houseilics (Musca domestica) were run by spraying the indicated formulation onto glass plates and allowing them to dry. The flies were confined over the plates, and percent kill was recorded 24 hours after confinement.

2 The tests on toxicity to mites (Tetram chus bimaculatus) were run by spraying horticultural (cranberry) bean plants infested with mites with the indicated formulation. Following trcatment, the plants were stored on racks in irrigated trays under greenhouse condition. Observations were made 2 or 3 days following spraying.

3 Vinyl phosphate compositions in the form of 25% crnulsifiable concentrates comprising 25% by weight vinyl phosphate compound (toxicant), 5% by weight Triton X-155 (21 commercial emulsifying agent comprising an alkyl aryl polycthcr alcohol) and by weight cyclohexauone.

4 Emulsified with 0.1% by weight of Triton X-155, a commercial alkyl aryl polyether alcohol.

6 4.8 grams of vinyl phosphate compound dissolved in acetone to cc.

While we have described the preferred embodiments for carrying out our invention, it will be apparent that many changes may be made without departing from the spirit of the invention.

We claim:

1. The process of combating insect and mite pests which comprises exposing said pests to a toxic amount of chlorofiuoro-substituted vinyl phosphate having the following formula:

in which R is alkyl containing from 1 to 4 carbon atoms, R is chlorofluorornethyl and R" is chlorofluoromethylene.

2. The process of combating insect and mite pests which comprises exposing said pests to a toxic amount of the chloroiluoro-substituted vinyl phosphate having the following formula:

(I? C 01213 (CH3O);PO-C

3. The process of combating insect and mite pests which comprises exposing said pests to a toxic amount of the chlorofluoro-substituted vinyl phosphate having the following formula:

COhF ll (C2H50)zP--OC c1, 4. Insecticidal and miticidal compositions comprising a toxic amount of a halo-substituted vinyl phosphate compound having the following formula:

(ROhii-O-C a halo-substituted vinyl phosphate compound having the following formula:

II (RO)2P0C in which R is alkyl containing from 1 to 4 carbon atoms, R is chlorofluoro-substit-uted methyl and R is a member of the group consisting of chloro-substit-uted methylene and chlorofluoro-substituted methylene.

6. Insecticidal and miticidal compositions comprising a ohlorofiuoro-substit'uted vinyl phosphate having the following formula:

[I (R0)2P0C in which R is alkyl containing from 1 to 4 carbon atoms, R is chloroflu-oromethyl and R is chlorofluoromethylene, together with a wetting agent and a carrier therefor.

7. Insecticidal and miticidal compositions comprising the chlorofluoro-su'bstituted vinyl phosphate having the following formula:

together with a wetting agent and a carrier therefor.

8. Insecticidal and miticidal compositions comprising the chlorofluoro-substi-tuted vinyl phosphate having the folowing formula:

CCli

together with a wetting agent and a carrier therefor.

References Cited by the Examiner UNITED STATES PATENTS 2,956,073 10/1960 Whetstone 16722 2,968,591 1/1961 Tracey 167i22 3,149,142 9/1964 Drysdale 167-22 JULIAN S. LEVI'IT, Primary Examiner.

S. I. FRIEDMAN, Assistant Examiner, 

1. THE PROCESS OF COMBATING INSECT AND MITE PESTS WHICH COMPRISES EXPOSING SAID PESTS TO A TOXIC AMOUNT OF CHLOROFLUORO-SUBSTITUTED VINYL PHOSPHATE HAVING THE FOLLOWING FORMULA: 